Isocyanates and process of preparing same



Unite States Patent ISOCYANATES AND PROCESS OF PREPARING SAME John C.Petropoulos, Norwalk, Conn., assignor to American Cyanamid Company, NewYork, N. Y., a corporation of Maine No Drawing. Application August 26,1957 Serial No. 680,385

Claims. (Cl. 260-77.5)

This-invention relates to a novel class of polymeric materials preparedby reacting a compound containing a plurality of active hydrogen atomswith certain isocyanato. isocyanatophenyl indans and to the process ofpreparing the same. More particularly, this invention relates to thepolymeric reaction products of compounds containing a plurality ofreactive hydrogen atoms with isocyanato isocyanatophenyl indans and/ orisothiocyanato isothiocyanatophenyl indans and to the process ofpreparing the same.

One of the objects of the present invention is to produce a polymericreaction product by reacting a compound containing a plurality of activehydrogen atoms with isocyanato isocyanatophenyl indans. A further objectof the present invention is to produce polymeric reaction productsprepared by reacting compounds containing a plurality of reactivehydrogen atoms such as polyhydric alcohols, polyamines, polyphenols, andthe like, with isocyanato isocyanatophenyl indans and to the process ofpreparing the same. These and other objects of the present inventionwill be discussed in greater detail hereinbelow.

The isocyanato isocyanatophenyl indans used in the present invention areprepared by reacting a phosgene such as phosgene per se or thiophosgenewith an amino aminophenyl indan. The amino aminophenyl indans areprepared by reducing the nitro nitrophenyl indans. The nitro nitrophenylindans may be prepared by reacting the dimers of an alpha substitutedstyrene with nitric acid wherein the substituent in the alpha positionis an alkyl group containing from 1 to 4 carbon atoms or a halo group.In order that the present invention may be fully understood, the methodsfor preparing each of the above substituted indans will be set forthhereinbelow starting with the dimerization of the substituted styrenesthrough the nitrate derivatives,amino derivatives and finally theisocyanato derivatives.

This application is a divisional application of my earlier filedapplication having the Serial No. 512,335

-filed May 31, 1955, entitled Isocyanates and Process of Preparing theSame which latter case is a continuationin-part of my earlier filedapplication having the Serial No. 414,860, filed March 8, 1954.

The starting materials utilized in the preparation of the isocyanatoisocyanatophenyl indans used in the present invention are substitutedstyrenes having an alkyl group or a halo group in the alpha position.The alkyl group in the alpha position may be any one of methyl, ethyl,propyl, and butyl. The halo group in the alpha position may be chloro,bromo, iodo or fiuoro. The ring positions may be either substituted orunsubstituted. If substituted, the substituents may be an alkyl groupcontaining between 1' and 4 carbon atoms or a halo group such as thosementioned above or both. Representative of the class of alkylsubstituted styrenes, which may be used in the practice of the processof the present invention are alpha methyl styrene, alpha ethyl styrene,alpha propyl styrene, alpha butyl styrene, alpha chloro Rte styrene,alpha bromo styrene, alpha, ortho dimethyl styrene, alpha,meta-dimethylstyrene, alpha, para-dimethylstyrene, alpha ethyl orthomethylstyrene, alpha ethyl meta methylstyrene, alpha ethylparamethylstyrene, alpha-propyl-ortho-methylstyrene, alphapropyl metamethylstyrene, alpha propyl paramethylstyrene,alpha-butyl-ortho-methylstyrene, alphabutyl meta methylstyrene, alphabutyl para-methylstyrene, alpha-chloro-meta-methylstyrene,alpha-bromopara butylstyrene, alpha iodo ortho propylstyrene,alpha-fluoro-para-ethylstyrene and the like.

In order that the process for the preparation of the dimers utilized inthe practice of the process of the present invention may be morecompletely understood, the following examples are set forth in which allparts are parts by weight unless otherwise indicated. These examples areset forth primarily for the purpose of illustration and any specificenumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appended claims.

DimerizatiOn of a,p-dimethylstyrene 800 parts of toluene cooled to 5 C.are introduced into a suitable reaction vessel. To the toluene, there lSadded 140 parts of a sulfuric acid. The mixture is stirred thoroughlyand maintained at a temperature of about 05 C. To the cooled mixture,there is added 260 parts of a,p-dimethylstyrene dissolved in 200 partsof toluene. The resulting mixture is allowed to react for /2 hour at 0-5C. and is then hydrolyzed with parts of water. The organic layer iswashed free of acidic material with water and is distilled to yield 250parts of a colorless oil having a boiling point of 142l44 C. at 0.8 mm.This oil solidifies and has a melting point of 3738 C. uncorrected.

Dimerization of u-ethyl-p-methylstyrene To 400 parts of toluene at 5 C.,there is added slowly 70 parts of 95% sulfuric acid followed by 144parts of a-ethyl-p-methylstyrene dissolved in 100 parts of toluene. Thetemperature is maintained at O10 C. during the entire addition. Theresulting mixture is allowed to react for /2 hour and then is hydrolyzedwith 100 parts of water. The organic material is collected, washed freeof acidic material with water and distilled to yield parts of acolorless liquid having a boiling point of 160-l65 C. at 1 mm.

Dimerization of u,meta-dimethylstyrene To 200 parts of toluene at 05 C.,there is added slowly 35 parts of 95% sulfuric acid, 65 parts of a,m-dimethylstyrene dissolved in 50 parts of toluene. The resultingmixture is allowed to react for about /2 hour and is then hydrolyzedwith water. The organic material is collected, Washed and distilled toyield 61 parts of a colorless liquid having a boiling point of 144-148C. at 1 mm. pressure.

Dimerization of crude a,p-dimethylstyrene To 368 parts of toluene at 10C., there is added slowly 50 parts of anhydrous aluminum chloride fol-'lowed by 516 parts of crude (undistilled) cap-dimethylstyrene dissolvedin 368 parts of toluene while maintaining the temperature below 10 C.After a 20-minute reaction time, the mixture is hydrolyzed with waterand the organic layer is collected and dried. The organic material isdistilled to give parts of a colorless oil having a boiling point ofl38l40 C. at 0.5-1 mm.

Dimerization of a,p-dimethylstyrene A mixture of 310 parts of freshlydistilled a,p-di-.

methylstyrene and 2 parts'of p-toluene sulfonic acid are heated in asteam bath for about 16 hours and then allowed to react at roomtemperature for 2 /2 months, at which time the p-toluene sulfonic acidcatalyst is removed by washing the organic layer with dilute sodiumbicarbonate solution. Distillation of the organic layer gave 151 partsof a very light yellow colored oil having a boiling point of 136140 C.at 1 mm. pressure.

By dimerizing alpha alkyl styrenes or alpha halo styrcnes in a mannercomparable to the examples set forth hereinabove, one could produce thefollowing indans which may then be nitrated by reaction with nitric acidto produce nitro nitro phenyl indans: 1- phenyl 1,3,3 trimethyl indan; 1phenyl 1,3 diethyl 3 methyl indan; 1 phenyl 1,3 dipropyl 3- methylindan; l phenyl 1,3 dibutyl 3 methylindan;1-phenyl-1,3-dichloro-3-methyl-indan; l-phenyl- 1,3 diiodo 3 methylindan; 1 phenyl 1,3-dibromo- 3 methyl indan; 1 phenyl 1,3 difluoro 3methylindan; 1 (4 methylphenyl) 1,3,3,6 tetramethylindan;l-(4-methylphenyl)-l,3-diethyl-3,6-dimethyl-indan, 1 (4 methylphenyl)1,3 dipropyl 3,6 dimethylindan; 1 (4 methylphenyl) 1,3 dibutyl 3,6dimethyl indan; l-(3 methylphenyl)-1,3,3,5-tetramethylindan; 1 (3methylphenyl) 1,3 diethyl 3,5 dimethyl indan; l (3 methylphenyl) 1,3dipropyl- 3,5 dimethyl indan; 1 (3 methylphenyl) 1,3 dibutyl 3,5dimethyl indan, 1 (3 methylphenyD- 1,3-dichloro-3,S-dimethyl-indan;1-(3-methylphenyl)-l,3- dibromo-3,5-dimethyl-indan and the like. 7

In order that the nitration of the indans be more completely understood,the following examples are set forth in which all parts are parts byweight unless otherwise indicated.

Method for the preparation of1-(4-methyl-3-nitrophenyl)-1,3,3,d-tetramethyl-5-nitr0-indan Into asuitable reaction vessel equipped with a thermometer and a stirrer,there is introduced 264 parts of1-(4-methylphenyl)-l,3,3,6-tetramethyl-indan and 750 parts ofchloroform. The charge is cooled to about to C. and there is added, insmall increments While constantly stirring, 396 parts of 96% sulfuricacid and 132 parts of 70.4% nitric acid. These acids are addedseparately but concurrently. The addition of these acids is maintainedat a rate of 3 parts of sulfuric per part of nitric acid. Thetemperature throughout the addition is held at 0-5 C. After the additionis completed, the reaction is permitted to continue for an additional 30minutes with constant stirring at the same temperature. The stirring isthen stopped and the reaction medium separates into two layers. Thechloroform layer is neutralized with sodium bicarbonate and thechloroform solution is then concentrated. On standing, pale yellowcrystals of 1-(4-methyl-3-nitrophenyl)-l,3,3,6-tetramethyI-S-nitro-indanform. The chloroform is filtered off and the nitro indan isrecrystallized from ethanol.

Preparation of1-(4-methyl-3-amin0phenyl)-1,3,3,6-tetramethyl-S-amino-indan 70.8 partsof l-(4-methyl-3-nitrophenyl)-l,3,3,6-tetramethyl-S-nitro-indan (0.2mol), 67 parts of iron powder (reduced) and 100 parts of 50% ethanol inwater are introduced into a suitable reaction vesesl equipped withstirrer, thermometer and reflux condenser. The charge is heated to thereflux temperature whereupon 5.2 parts of concentrated hydrochloric acidin 25 parts of a 50% aqueous solution of ethanol is added slowly. Afterthe addition of the acid solution, the charge is reacted for about 2hours at reflux. After this two hour heating period, suflicientalcoholic potassium hydroxide to neutralize the acid present in thecharge is added and the resultant syrup is filtered hot. The ironprecipitate is Washed with ethanol and 84 parts of 6 N sulfuric acid areadded to the filtrate. Light orange crystals precipitate which have amelting point of 238-241 C. The

4 crystalline precipitate comprising the sulfate salt of the diamine ismixed with 200 parts of water and parts of 6 N sodium hydroxide and themixture is heated to reflux, whereupon suflicient ethanol is added togive a clear solution. This solution is then refluxed for 1 hour. Thesolution is cooled and poured into ice water, a light pink precipitateforms. The precipitate is filtered and Washed with water until neutral.A light tan sticky solid results which is distilled under vacuum, givinga light yellow liquid which hardens to an amorphous material. Thediamino indan produced distilled at 188- 189 C. at 0.3 mm. of mercury or207-208 C. at 0.8 mm. of mercury. The yield was 36 parts, representing61% of theoretical. The melting point was 90.5-92 C., uncorrected.

Method for the preparation of 1-(4-methyl-3-is0cyanat0- phenyl)-1,3,3,6-zetramethyl-S-isocyanato-indan A solution of 40 parts of drytoluene saturated with phosgene at 0-3 C. is prepared and there is addedthereto with constant stirring, 5 parts of 1-(4-methyl-3- aminophenyl)l,3,3,6 tetramethyl 5 amino-indan dissolved in dry toluene. A fine whiteprecipitate forms. The charge is heated to 55-60 C. in /2 hour,whereupon a steady stream of phosgene is passed through the reactionmixture. After 20 minutes at 55-60 C., the mixture clears to ayellowish-green solution and the mixture is then brought to reflux.Reflux starts at about 102 C. and is continued for about 2 hours,whereupon the reflux temperature had risen to 109 C. The phosgene streamis then stopped and the solution refluxed for an additional 45 minutes.The toluene is distilled off at atmospheric pressure. When the solutionhas concentrated to about 10-15 parts, the remainder is distilled undervacuum. 3 parts of 1 (4 methyl-3-isocyanatophenyl)-l,3,3,6-tetramethyl-5-isocyanato-indan is produced,which is a pale yellow viscous liquid having a boiling point of 168 C.at 0.2 mm. of mercury. The yield is 51% of theoretical. On standing, thediisocyanato derivative crystallizes out and is recrystallized fromheptane giving a white crystalline material with a melting point of 7779C., uncorrected.

Preparation of 1-(4-methyl-3-isothiocyanatophenyl)-1,3,3,6-tezramethyl-5-isothiocyanato-indan The preceding example is repeatedin substantially all details except that in the place of the phosgenethere is utilized thiophosgeue in equivalent amounts.

Preparation of 1-(4-nitr0phenyl)-1,3,3-trimethyl-6-nitroindan 176 partsof 1,3,3-trimethyl-l-phenyl-indan (0.75 mol) are dissolved in 750 partsof chloroform. To this solution there is added in small increments, 297parts of 96% sulfuric acid and 99 parts of 70.4% nitric acid whilemaintaining a temperature at about O5 C. during the increment addition.The reaction is permitted to continue for about 3 hours at 0-5 C., afterthe addition of the mixture of the acids. The chloroform layer is thenseparated from the acid layer and washed with water and sodiumbicarbonate until neutral. Crystallization is induced by scratching.Upon recrystallization from isopropanol, there is produced a pale yellowproduct that melts at 149.5-151 C.

Process for the preparation of 1-(4-amin0phenyl)-1,3,3-trimethyl-6-amin0-ina'an 32.6 parts of1-(4-nitrophenyl)-1,3,3-trimethyl-6-nitroindan, 33.5 parts of ironpowder (reduced) and 50 parts of a 50% aqueous solution of ethanol areintroduced into a suitable reaction vessel equipped with thermometer,stirrer and reflux condenser. The charge is then heated to reflux. Atreflux, there is added 2.6 parts of concentrated hydrochloric acid in12.5 parts of a 50% aqueous solution of ethyl alcohol slowly. Reactionis continued for about 2 hours after the addition is completed a'treflux temperature. The charge is then neutralized with a slight excessof alcoholic potassium hydroxide. ethyl alcohol.

lPreparation of 1-(4-isocyanat0phenyl)-1,3,3-trimethyl-6-isocyanato-indan 8 parts of1-(4-arninophenyl)-1,3,3-trimethyl-6-aminoindan are dissolved in 35parts of dry toluene and the solution is added slowly to a solution of24 parts of phosgene in 52 parts of dry toluene at C. The temperature ofthe charge is maintained at 0-3 C. during the addition. On completion ofthe addition, the mixture is heated gradually to about 55-6() C. inabout 40 minutes at which time a steady stream of phosgene is fed intothe system. When the mixture had cleared from milky white to a clear,pale yellow solution (in about 30 minutes), the temperature is increasedto reflux. After about 1 hour at the reflux temperature, the phosgenestream is shut off and the reaction continued at reflux for anadditional 30 minutes. The toluene is then stripped oif leaving aviscous orange syrup. The material crystallized on cooling. Thediisocyanato indan was recrystallized from hexane to give a solidmaterial having a melting point of 90-93 C. Infra-red analysis confirmedthe anticipated structure.

Preparation of 1(4-isothiocynnatophenyl)-1,3,3-trimethyl-6-isothiocyanato-indan Thepreceding example is repeated in every essential detail except that inthe place of phosgene, there is substituted an equivalent amount ofthiophosgene.

In the preparation of the isocyanato isocyanato indans, the followingdinitro indans may be utilized as intermediates: 1 (4 methyl 3nitrophenyl) 1,3,3,6 tetrarnethyI-S-nitro-indan; 1(4-ethyl-3-nitrophenyl)-1,3,3-trimethyl 6 ethyl 5 nitro indan; 1 (4propyl 3- :nitrophenyl)-1,3,3-trimethyl-6-propyl-5-nitro-indan; 1-(4-butyl 3 nitrophenyl) 1,3,3 trimethyl 6 butyl 5- nitro-indan;l-(4-chloro-3-nitropheny1)-1,3,3-trimethyl-6- chloro 5 nitro indan; l (4bromo 3 nitrophenyl) 1,3,3 trimethyl 6 bromo 5 nitro indan; 1-(4-nitrophenyl) -1,3 ,3-trimethyl-6-nitro-indan; 1-( 3-nitrophenyl) -1,3,3-trimethyl-5nitro-indan; 1- Z-nitrophenyl)1,3,3-trimethyl-4-nitro-indan; 1-(4-methyl-3-nitrophenyl)- 1,3 diethyl3,6 dimethyl 5 nitro indan; 1 (4- methyl 3 nitrophenyl) 1,3 dipropyl 3,6dimethyl- 5-nitro-indan; 1-(4-n1ethyl-3-nitrophenyl l ,3-dibutyl-3,6-dimethyl-S-nitro-indan; 1- (4-methyl-3-nitrophenyl l ,3- diohloro 3,6dimethyl 5 nitro indan; 1 (4 methyl 3 nitrophenyl) 1,3 diiodo 3,6dimethyl 5- nitro-indan, and the like.

Amongst diamino indans which may be used to prepare the diisocyanatoindans of the present invention are the following:1-(4-methyl-3-arninophenyl) -1,3,3,6-tetramethyI-S-amino-indan;1-(4-ethyl-3-aminophenyl)-1,3,3- trimethyl 6 ethyl 5 amino indan; 1 (4propyl- 3 aminophenyl) 1,3,3 trimethyl 6 propyl 5 -amino indan; 1 (4butyl 3 aminophenyl) 1,3,3 trimethyl 6 butyl 5 amino indan; 1 (4 chloro3- aminophenyl 1,3,3 trimethyl 6 chloro-5-amino-indan;

1 (4 -.bromo 3 aminophenyl) 1,3,3-trimethyl 6- bromo 5 amino indan; l (4aminophenyl) 1,3,3- trimethyl 6 amino indan; 1 (3 aminophenyl)-1,3,3-trimethyl 5 amino indan; 1 (2 aminophenyl)-1,3,3-trimethyl 4 aminoindan; 1 (4 methyl 3- aminophenyl) 1,3 diethyl 3,6 dimethyl 5aminoindan; l (4 methyl 3 aminophenyl) 1,3 dipropyl- 3,6-dimethy1 5amino-indan; 1 (4 methyl 3 aminophenyl) 1,3 dibutyl 3,6 dimethyl 5aminoindan; 1 (4 methyl 3 aminophenyl) 1,3 dichloro 3,6 dimethyl 5amino-indan; 1 (4 methyl 3aminophenyl)-l,3-diiodo-3,6-dimethyl-5-amino-indan, and the like.

Amongst the diisocyanato indans which may be prepared in accordance withthe present invention are the following: 1 (4 methyl 3 isocyanatophenyl)1,3, 3,6 tetramethyl 5 isocyanato indan; 1 (4 ethyl- 3 isocyanatophenyl)1,3,3 trimethyl 6 ethyl 5- isocyanato indan; 1 (4 propyl 3isocyanatophenyl) 1,3,3 trimethyl 6 propyl 5 isocyanato indan; 1 (4butyl 3 isocyanatophenyl) 1,3,3 trimethyl- 6 butyl 5 isocyanato indan; 1(4 chloro 3 isocyanatophenyl) 1,3,3 trimethyl 6 chloro 5 isocyanatoindan; 1 (4 bromo 3 isocyanatophenyl)- 1,3,3 trimethyl 6 bromo 5isocyanato indan; 1 (4 isocyanatophenyl) 1,3,3 trimethyl 6 isocyanatoindan; 1 (3 isocyanatophenyl) 1,3,3 trimethyl 5 isocyanato indan; 1 (2isocyanatophenyl) 1,3,3 trimethyl 4 isocyanatoindan; 1 (4- methyl 3isocyanatophenyl) 1,3 diethyl 3,6 dimethyl 5 isocyanato indan; 1 (4methyl 3 isocyanatophenyl) 1,3 dipropyl 3,6 dimethyl 5 isocyanato indan;1 (4 methyl 3 isocyanatophenyl)- 1,3 dibutyl 3,6 dimethyl 5 isocyanatoindan; l- (4 methyl 3 isocyanatophenyl) 1,3 dichloro 3,6- dirnethyl 5isocyanato indan; 1 (4 methyl 3 isocyanatophenyl) 1,3 diiodo 3,6dimethyl 5 isocyanato indan; 1 (4 methyl 3 isothiocyanatophenyl) 1,3,3,6tetramethyl 5 isothiocyanato indan; 1 (4 ethyl 3 thiocyanatop'henyl)1,3,3 trimethyl- 6 ethyl 5 isothiocyanato indan; 1 (4 propyl 3-isothiocyanatophenyl) 1,3,3 trimethyl 6 propyl 5- isothiocyanato indan;l (4 butyl 3 isothiocyanatophenyl) 1,3,3 trimethyl 6 butyl 5isothiocyanatoindan; l (4 chloro 3 isothiocyanatophenyl) 1,3,3-trimethyl 6 chloro 5 isothiocyanato indan; 1 (4- bromo 3isothiocyanatophenyl) 1,3,3 trimethyl 6- bromo 5 isothiocyanato indan; 1(4 isothiocyanatophenyl) 1,3,3 trimethyl 6 isothiocyanato indan; 1 (3isothiocyanatophenyl) 1,3,3-trimethyl 5 isothiocyanato indan; 1 (2isothiocyanatophenyl) 1,3, 3 trimethyl 4 isothiocyanato indan; 1 (4methyl- 3 thiocyanatophenyl) 1,3 diethyl 3,6 dimethyl 5- isothiocyanatoindan; 1 (4 methyl 3 isothiocyanatophenyl) 1,3 dipropyl 3,6 dimethyl 5isothiocyanato indan; l (4 methyl 3 isothiocyanato)- 1,3 dibutyl 3,6dimethyl 5 isothiocyanato indan; 1 (4 methyl 3 isothiocyanatophenyl) 1,3dichloro- 3,6 dimethyl 5 isothiocyanato indan; 1 (4 methly 3isothiocyanatophenyl) 1,3 diiodo 3,6 dimethyl-S-is0thiocyanato-indan,and the like.

The diisocyanato indans and the diisothiocyanato indans disclosed hereinabove have been found to be exceedingly useful in preparing polymericmaterials by reacting the same with a compound having a plurality ofactive hydrogen atoms. For instance, these cyanato indans may be used inresinous compositions such as unsaturated polyester resinouscompositions where a foamed resinous material is desired. Theseunsaturated polyester resinous compositions are illustrated inconsiderable detail in the U. 8. Patents 2,255,313, 2,409,633,2,443,735-41, inclusive, and 2,510,503. Additionally, the diisocyanatoand dithiocyanato indans of the present invention may be utilized incoreaction with alcohols such as polyhydric alcohols; amines, such aspolyamines, phenols, such as polyphenols and polycarboxylic acids toform resinous materials. These resinous materials may be used for theproduction of coating compositions, laminating compositions, moldingcompositions, castings, adhesives and the like.

Among the polyhydric alcohols which may be reacted With the isocyanatoindans of the present invention are ethylene glycol, diethylene glycol,trimethylene glycol, tetramethylene glycol, trimethylol ethane,trimethylol propane, glycerol, pinacol, arabitol, xylitol, adonitol,mannitol, sorbitol, pentaerythritol, di-pe'ntaerythritol or anypolyhydric alcohols shown in my copending application having the SerialNo. 489,793, filed February 21, 1955, and the like. In reacting withthese diisocyanato indans, these polyhydric alcohols may be used eithersingly or in combination with one another.

' Among the polyamines which may be used to form resinous materials byreacting with the diisocyanato indans of the present invention areethylene diamine, diethylene triamine, triethylene tetramine,tetraethylene pentamine, 3,3 iminobispropylamine, tris (3 aminopropyl)amine, N,N-(2-hydroxyethyl-2'-aminoethyl) amine,N,N-(3-hydroxypropyl-3'-aminopropyl) amine, or any of the diamino indansshown hereinabove.

Among the diphenols that may be used to form resinous materials byreaction with the dicyandiamide indans of the present invention are'p,p'-dihydroxy diphenyl dimethyl methane, p,p'-dihydroxybenzophenone,-p,p-dihydroxy diphenyl or any of the diphenols shown in mycopending application having the Serial No. 443,971, filed July 16,1954. These diphenols may be used either singly or in combination withone another.

In the preparation of the diisocyanato indans used in the presentinvention, one should react more than two mols of phosgene orthiophosgene per mol of diamino indan. This reaction may be carried outover a rather wide range of temperatures such as between about 40 C. andreflux. Ordinarily, it is preferred that the reaction be carried out inthe presence of an inert organic solvent such as benzene, toluene,xylene, kerosene, dichlorobenzene or mineral spirits such as Varsol No.1, Varsol No. 2 and the like. For best yields, it is preferred to carryout the reaction at a relatively low temperature such as between aboutC. and +10 C. during the initial portion of the reaction While insuringthat an excess amount of phosgene or thiophosgene is present in thesphere of reaction. The temperature may then be increased graduallywhile continuing to pass the phosgene gas through the system and finallyheating at reflux temperatures to complete the reaction. When thereaction is completed, the solvent is distilled off and the residue maybe washed, crystallized and even recrystallized to produce a purediisocyanato derivative. The reaction may be carried out eitherbatch-wise or by continuous operation and in the latter instance, itwill be possible to recycle materials such as the phosgene. If desired,one can form the hydrochloride salt of the diamino indan and said saltcan be reacted with the phosgene or thiophosgene to produce thediisocyanato derivative.

In order to illustrate the preparation of resinous materials using theisocyanato indan of the present invention, the following examples areset forth in which all parts are parts by weight. These examples are setforth primarily for the purpose of illustration and any specificenumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appended claims.

Example 1 Into a suitable reaction vessel equipped with thermometer, andstirrer, there is introduced 60.5 parts of 1-(4- isocyanatophenyl)-1,3,3 -trimethyl-6-isocyanato-indan dissolved in 1,000 parts of heptane andthere is added thereto, in small increments, 12.9 parts of trimethylenediamine. Exothermic reaction occurs with immediate formation of a whiteprecipitate, which had the following properties: Softening point, 210C.; melting point, 230240 C.

Example 2 Into a suitable reaction vessel equipped with thermometer,stirrer and reflux condenser, there is introduced 31.8 parts of1-(4-isocyanatophenyl)-1,3,3-trimethyl-6- isocyanato-indan in 1200 partsof heptane. There is added thereto 6.2 parts of ethylene glycol. Thereactants are heated gradually to reflux and held at that temperaturefor about 5 minutes. A light brown precipitate forms which has asoftening point of 165 C.

Example 3 31.8 parts of 1-(4-isocyanatophenyl)-1,3,3-trirnethyl-6-isocyanato-indan in 600 parts of methyl ethyl ketone are introduced intoa suitable reaction vessel equipped with thermometer, stirrer and refluxcondenser. There is added thereto 14.6 parts of adipic acid. The chargeis heated gradually to the reflux temperature and held at thattemperature for about 10 minutes. The solvent is then stripped off. Oncooling, a crystalline material is produced which melts at 145-160 C. toa viscous melt and remained a viscous melt with some decomposition up to280 C.

Example 4 34.6 parts of 1-(4-methyl-3-isocyanatophenyl)-1,3,3,6-tetramethyl-S-isocyanato-indan are dissolved in parts of heptane. 7.4parts of trimethylene diamine are added. The polyurea which formsprecipitates from solution as a white powderous material.

Example 5 34.6 parts of 1-(4-methyl-3-isocyanatophenyl)-1,3,3,6-tetramethyl-S-isocyanato-indan are dissolved in 100 parts of heptane.6.2 parts of ethylene glycol are added. The polyurethane, which forms,precipitates from solution on standing.

Example 6 100 parts of polyethylene adipate (hydroxyl number equals 50)are heated to C., whereupon 10 parts of 1 (4 methyl 3 isocyanatophenyl)1,3,3,6 tetrarnethyl-5-isocyanato-indan are added. The reaction mixtureis heated for 20 minutes at 110120 C. At the end of the reaction time, 1part of tolylene diamine is added. The viscosity increases almost to agel. The product is cured by heating the mass for 1 hour at C. Theresultant product is a tough, rubbery sheet.

Generally speaking, the diisocyanato indans of the present invention,including the diisothiocyanato indans, may be reacted with any compoundcontaining an active hydrogen atom W ich includes compounds which arecapable of substitution by a metal. For polymeric purposes, thesecompounds should contain at least two active hydrogen atoms. In additionto those set forth hereinabove, there is included such compounds aswater, amides, anhydrides, ammonia, Grignard reagents, and the like.

I claim:

1. A process comprising reacting a compound having a plurality of activehydrogen atoms with a compound having the general formula:

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon atoms, and a halo group, R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group, and X is a memberselected from the group consisting of S and O to produce a resinousmaterial.

2. A process comprising reacting a compound having a 9 plnrality'ofactive hydrogen atoms with a compound having the'general formula:

. ocN' om Noo wherein R and R are members selected from the groupconsisting of H, an alkyl group containing 1 to 4 carbon atoms, and ahalo group, R and R are members selected from the group consisting of analkyl group containing 1 to 4 carbon atoms, and a halo group to producea resinous material.

3. A process comprising reacting a compound having a plurality of activehydrogen atoms with a compound having the general formula:

SUN (3' C/CH2 NOS wherein R and R are members selected from the groupconsisting of H, an alkyl group containing 1 to 4 carbon atoms, and ahalo group, R and R are members selected from the group consisting of analkyl group containing 1 to 4 carbon atoms, and a halo group to producea resinous material.

4. A process comprising reacting a compound having a plurality of activehydrogen atoms with1-(3-isocyanatophenyl)-1,3,3-trimethyl-5-isocyanato-indan to produce aresinous material.

5. A process comprising reacting a compound having a plurality of activehydrogen atoms withl-(3-isothiocyanatophenyl)-1,3,3-trimethyl-S-isothiocyanato-indan toproduce a resinous material.

6. A process comprising reacting a polyhydric alcohol with a compoundhaving the general formula:

XCN CH5 C CH NCX

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon atoms, and a halo group, R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group, and X is a memberselected from the group consisting of S and O to produce a resinousmaterial.

7. A process comprising reacting a polyaminewith a compound having thegeneral formula:

XCN CH3 XGN OH:

crr2 \R3 N ox wherein R and R are members selected from the groupconsisting of H, an alkyl group containing 1 to 4 carbon atoms, and ahalo group, R and R are members selected from the group consisting of analkyl group con-- taining 1 to 4 carbon atoms, and a halo group, and Xis a member selected from the group consisting of S and 0..

9. The resinous reaction product of a compound having a plurality ofactive hydrogen atoms with a compound having the general formula:

wherein R and R are members selected from the g roup consisting of H, analkyl group containing 1 to 4 carbon atoms, and a halo group, R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group.

10. The resinous reaction product of a compound having a plurality ofreactive hydrogen atoms with a com-' pound having the general formula:

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon 1-1 atoms, and a halo group, R andR are members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group.

11. The resinous reaction product of a compound having a plurality ofreactive hydrogen atoms with 1-(3-isocyanatophenyl) l ,3,3-trimethyl-S-isocyanato-indan.

12. The resinous reaction product of a compound having a plurality ofreactive hydrogen atoms With 1-(3-isothiocyanatophenyl) 1,3,3 trimethyl5 isothiocyanato-indan.

13. The resinous reaction product of a polyhydric alcohol with1-(3-isocyanatophenyl)-1,3,3-trimethy1-5- isocyanato-indan.

1'2 14. The resinous reaction product of a polyamine with1-(3-isocyanatophenyl)-1,3,3-trimethy1 5 .isocyanatoindan.

15. The resinous reaction product of a polyamine with1-(3-isothiocyanatophenyl)-1,3,3-trimethy1- 5 isothiocyanato-indan.

References Cited in the file of this patent UNITED STATES PATENTS UNITEDSTATES- PATENT OFFICE CERTIFICATE OF CORRECTION Pat entNo. 2,855,385October 7, 1958 John C. Petropoulos It is' hereby certified that errorappears in the printed specification of the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 3, line 63, for "vesesl" read me vessel column 5, line 66, for"aminophenyl-=" read m aminophenyl)- column 6, line 31, for"l-(4-ethyl-3-=thiocyanatophenyl) read l-(4 line 44, for"3==thiocyanatophenyl) read 3=isothiocyanatophenyl) 1 50 and 51, for"-methly=3= isothiocyanatophenyl) read -=methyl-3=-isLothiocyanatophenyl) lines Signed and sealed, this 30th day ofDecember l958.

SEAL) that:

KARL= H. AXLINE Attesting; Officer ROBERT C. WATSO N Cunninioner ofPatents -ethyl-3==isothiocyanatophenyl)

1. A PROCESS COMPRISING REACTING A COMPOUND HAVING A PLURALITY OF ACTIVEHYDROGEN ATOMS WITH A COMPOUND HAVING THE GENERAL FORMULA: